Solid oxide electrolysis cells hold unique Faraday efficiency and favored thermodynamic/kinetics for CO2 reduction to CO. Perovskite oxide-based composite materials are promising alternatives to Ni-based cermet electrodes in SOECs. However, contrary results of the electrocatalytic activity over single-phase perovskite oxide exist and the rationale of the negative effect is not well revealed. In this work, two-phase perovskite materials with various complementary properties and unique interfaces are self-assembled, which was realized by "subtractive" defect-driven phase separation. The obtained heterostructure electrodes showed reduced performance over that of single-phase materials although the cyclic stability was improved. The main reasons for the performance degradation are the decrease of electrical conductivity, oxygen vacancy concentration while increasing the average valence state of B-site Fe cations, and electrode surface Sr aggregation. This work highlights the self-assembly method and insight into the rational design and synthesis of active electrodes/catalysts for CO2 conversion in solid oxide cells.
Solid oxide electrolysis cells (SOECs) hold enormous potential for efficient conversion of CO2 to CO at low cost and high reaction kinetics. The identification of active cathodes is highly desirable to promote the SOEC's performance. This study explores a lithium-doped perovskite La0.6- x Lix Sr0.4 Co0.7 Mn0.3 O3-δ (x = 0, 0.025 0.05, and 0.10) material with in situ generated A-site deficiency and surface carbonate as SOEC cathodes for CO2 reduction. The experimental results indicate that the SOEC with the La0.55 Li0.05 Sr0.4 Co0.7 Mn0.3 O3-δ cathode exhibits a current density of 0.991 A cm-2 at 1.5 V/800 °C, which is an improvement of ≈30% over the pristine sample. Furthermore, SOECs based on the proposed cathode demonstrate excellent stability over 300 h for pure CO2 electrolysis. The addition of lithium with high basicity, low valance, and small radius, coupled with A-site deficiency, promotes the formation of oxygen vacancy and modifies the electronic structure of active sites, thus enhancing CO2 adsorption, dissociation process, and CO desorption steps as corroborated by the experimental analysis and the density functional theory calculation. It is further confirmed that Li-ion migration to the cathode surface forms carbonate and consequently provides the perovskite cathode with an impressive anti-carbon deposition capability, as well as electrolysis activity.
A semiconductor-ionic fuel cell (SIFC) is recognized as a promising technology and an alternative approach to reduce the operating temperature of solid oxide fuel cells. The development of alternative semiconductors substituting easily reduced transition metal oxide is a great challenge as high activity and durability should be satisfied simultaneously. In this study, the B-site Ni-doped La0.2Sr0.7Ti0.9Ni0.1O3-δ (LSTN) perovskite is synthesized and used as a potential semiconductor for SIFC. The in situ exsolution and A-site deficiency strategy enable the homogeneous decoration of Ni/NiO nanoparticles as reactive sites to improve the electrode reaction kinetics. It also supports the formation of basic ingredient of the Schottky junction to improve the charge separation efficiency. Furthermore, additional symmetric Ni0.8Co0.15Al0.05LiO2-δ (NCAL) electrocatalytic electrode layers significantly enhance the electrode reaction activity and cells' charge separation efficiency, as confirmed by the superior open circuit voltage of 1.13 V (close to Nernst's theoretical value) and peak power density of 650 mW cm-2 at 550 °C, where the latter is one order of magnitude higher than NCAL electrode-free SIFC. Additionally, a bulk heterojunction effect is proposed to illustrate the electron-blocking and ion-promoting processes of the semiconductor-ionic composite electrolyte in SIFCs, based on the energy band values of the applied materials. Overall, we found that the energy conversion efficiency of novel SIFC can be remarkably improved through in situ exsolution and intentional introduction of the catalytic functionality.
Hydrogen is the alternative renewable energy source for addressing the energy crisis, global warming, and climate change. Hydrogen is mostly obtained in the industrial process by steam reforming of natural gas. In the present work, CuCrO2 particles were attached to the surfaces of electrospun CeO2 nanofibers to form CeO2-CuCrO2 nanofibers. However, the CuCrO2 particles did not readily adhere to the surfaces of the CeO2 nanofibers, so a trace amount of SiO2 was added to the surfaces to make them hydrophilic. After the SiO2 modification, the CeO2 nanofibers were immersed in Cu-Cr-O precursor and annealed in a vacuum atmosphere to form CeO2-CuCrO2 nanofibers. The CuCrO2, CeO2, and CeO2-CuCrO2 nanofibers were examined by X-ray diffraction analysis, transmission electron microscopy, field emission scanning electron microscopy, scanning transmission electron microscope, thermogravimetric analysis, and Brunauer-Emmett-Teller studies (BET). The BET surface area of the CeO2-CuCrO2 nanofibers was 15.06 m2/g. The CeO2-CuCrO2 nanofibers exhibited hydrogen generation rates of up to 1335.16 mL min-1 g-cat-1 at 773 K. Furthermore, the CeO2-CuCrO2 nanofibers produced more hydrogen at lower temperatures. The hydrogen generation performance of these CeO2-CuCrO2 nanofibers could be of great importance in industry and have an economic impact.
Reversible solid oxide cells (RSOCs) can efficiently render the mutual conversion between electricity and chemicals, for example, electrolyzing CO2 to CO under a solid oxide electrolysis cell (SOEC) mode and oxidizing CO to CO2 under a solid oxide fuel cell (SOFC) mode. Nevertheless, the development of RSOCs is still hindered, owing to the lack of catalytically active and carbon-tolerant fuel electrodes. For improving mutual CO-CO2 conversion kinetics in RSOCs, here, we demonstrate a high-performing and durable fuel electrode consisting of redox-stable Sr2(Fe, Mo)2O6-δ perovskite oxide and epitaxially endogenous NiFe alloy nanoparticles. The electrochemical impedance spectrum (EIS) and distribution of relaxation time (DRT) analyses reveal that surface/interface oxygen exchange kinetics and the CO/CO2 activation process are both greatly accelerated. The assembled single cell produces a maximum power density (MPD) of 443 mW cm-2 at 800 °C under the SOFC mode, with the corresponding CO oxidation rate of 5.524 mL min-1 cm-2. On the other hand, a current density of -0.877 A cm-2 is achieved at 1.46 V under the SOEC mode, equivalent to a CO2 reduction rate of 6.108 mL min cm-2. Furthermore, reliable reversible conversion of CO-CO2 is proven with no performance degradation in 20 cycles under SOEC (1.3 V) and SOFC (0.6 V) modes. Therefore, our work provides an alternative way for designing highly active and durable fuel electrodes for RSOC applications.
Fuel cells are highly efficient and green power sources. The typical membrane electrode assembly is necessary for common electrochemical devices. Recent research and development in solid oxide fuel cells have opened up many new opportunities based on the semiconductor or its heterostructure materials. Semiconductor-based fuel cells (SBFCs) realize the fuel cell functionality in a much more straightforward way. This work aims to discuss new strategies and scientific principles of SBFCs by reviewing various novel junction types/interfaces, i.e., bulk and planar p-n junction, Schottky junction, and n-i type interface contact. New designing methodologies of SBFCs from energy band/alignment and built-in electric field (BIEF), which block the internal electronic transport while assisting interfacial superionic transport and subsequently enhance device performance, are comprehensively reviewed. This work highlights the recent advances of SBFCs and provides new methodology and understanding with significant importance for both fundamental and applied R&D on new-generation fuel cell materials and technologies.
Single-layer fuel cells (SLFCs) based on mixed semiconductors and ionic conductors demonstrate simplified material preparation and fabrication procedure and possess high performance potentially. However, the operational stability and principle of SLFCs have not yet been convinced of either commercialization or fundamental interests. We hereby report on the employment of a perovskite oxide-based phase-structured redox-stable semiconductor prior to determining a possible solution that improves the durability of the SLFC. Feasible working principles are established and an in-depth understanding of the short-circuit-free phenomenon in SLFCs with the mixed ionic and electronic conductors is provided. Additionally, a smart material design and cell structure processing are also proposed. An extended nonstop testing period of up to 2 days confirms the project feasibility and improved durability of the SLFCs, achieved by replacing the unstable lithiated oxide phase with redox-stable perovskite oxide, though the electrochemical performance is sacrificed. The precipitated metal/alloy nanoparticle on perovskite oxide not only improves the electrode reaction kinetics but also facilitates the charge separation and ionic conduction in SLFCs, consequently enhancing the fuel cell performance and electrical efficiency. The results confirmed the potential of stable operation for future practical deployment of SLFCs via appropriate selection of material and cell structure design. It is greatly believed that the physical junction plays a crucial role in overcoming the internal short-circuit issue of SLFCs.
A facile route to scalable production of N and S co-doped, hierarchically porous carbon nanofiber (NSHCF) membranes (ca. 400â cm2 membrane in a single process) is reported. As-synthesized NSHCF membranes are flexible and free-standing, allowing their direct use as cathodes for efficient electrochemical CO2 reduction reaction (CO2 RR). Notably, CO with 94 % Faradaic efficiency and -103â mA cm-2 current density are readily achieved with only about 1.2â mg catalyst loading, which are among the best results ever obtained by metal-free CO2 RR catalysts. On the basis of control experiments and DFT calculations, such outstanding CO Faradaic efficiency can be attributed to the co-doped pyridinic N and carbon-bonded S atoms, which effectively decrease the Gibbs free energy of key *COOH intermediate. Furthermore, hierarchically porous structures of NSHCF membranes impart a much higher density of accessible active sites for CO2 RR, leading to the ultra-high current density.
Nonprecious transition metal phosphides (TMPs) have emerged as robust electrocalysts for the hydrogen evolution reaction (HER). However, the TMPs suffer from low activity for water dissociation, which greatly limits the efficiency for alkaline HER. Here, a facile yet robust strategy is reported to boost the HER of metal phosphides by coating defective TiO2 overlayers. The oxygen vacancies (Ov ) on defective TiO2 overlayers are found to possess high activity for adsorption and dissociation of water, thereby significantly promoting the initial Volmer step of HER to generate the reactive hydrogen atoms. Moreover, the porous (Co, Ni)2 P (i.e., Co2 P and Ni2 P) nanosheets provide enough active sites for adsorption and recombination of reactive hydrogen atoms to produce hydrogen gas. The catalytic synergy of (Co, Ni)2 P and Ov coupled with the hierarchically porous structure renders the porous (Co, Ni)2 P@0.1TiO2 nanosheet arrays excellent electrocatalysts for HER, showing a small overpotential (92 mV) to yield a current density of 10 mA cm-2 , a small Tafel slope (49 mV dec-1 ), and an outstanding stability. This work demonstrates a surface decoration route for enhancing the activity of nonprecious metal-based electrocatalysts for HER.
Fabricating heterointerfaces with optimized electronic structures is a robust strategy to boost the activity of electrocatalysts. Herein, for the first time, we demonstrate that the heterointerfaces of metallic Ag and NiFe-oxides on hierarchical nanoarrays facilitate the charge transfer during the OER and optimize the electronic state of NiFe-oxides, thereby significantly boosting the activity for the OER.
Numerous catalysts have been successfully introduced for CO2 fixation in aqueous or organic systems. However, a single catalyst showing activity in both solvent types is still rare, to the best of our knowledge. We developed a core-shell-structured AgNW/NC700 composite using a Ag nanowire (NW) core encapsulated by a N-doped carbon (NC) shell at 700 °C. Through control experiments and density functional theory calculations, it was confirmed that Ag nanowires acted as the active sites for CO2 fixation and the uniformly coating of N-doped carbon created a CO2 -rich environment around the Ag nanowires, which could significantly improve the catalytic activity of Ag nanowires for electrochemical CO2 fixation. Under mild conditions, up to 96 % faradaic efficiency of CO, 95 % yield of Ibuprofen and 92 % yield of propylene carbonate could be obtained in the electrochemical CO2 direct reduction, carboxylation and cycloaddition, respectively, using the same AgNWs/NC700 catalyst. These results might provide an alternative strategy for efficient electrochemical fixation of CO2 .
A novel Pt-NP@NCNF@CC composite was prepared by the electrospinning technique. It is a highly efficient and binder-free catalyst for the direct reduction and carboxylation of CO2 with halides. Formate with 91% Faradaic efficiency and 2-phenylpropionic acid with 99% yield could be obtained, respectively. Moreover, this catalyst has excellent stability and reusability.
Sufficiently high oxygen ion conductivity of electrolyte is critical for good performance of low-temperature solid oxide fuel cells (LT-SOFCs). Notably, material conductivity, reliability, and manufacturing cost are the major barriers hindering LT-SOFC commercialization. Generally, surface properties control the physical and chemical functionalities of materials. Hereby, we report a Sm3+, Pr3+, and Nd3+ triple-doped ceria, exhibiting the highest ionic conductivity among reported doped-ceria oxides, 0.125 S cm-1 at 600 °C. It was designed using a two-step wet-chemical coprecipitation method to realize a desired doping for Sm3+ at the bulk and Pr3+/Nd3+ at surface domains (abbreviated as PNSDC). The redox couple Pr3+/Pr4+ contributes to the extraordinary ionic conductivity. Moreover, the mechanism for ionic conductivity enhancement is demonstrated. The above findings reveal that a joint bulk and surface doping methodology for ceria is a feasible approach to develop new oxide-ion conductors with high impacts on advanced LT-SOFCs.
In this work we report a porous silver thin film cathode that was fabricated by a simple inkjet printing process for low-temperature solid oxide fuel cell applications. The electrochemical performance of the inkjet-printed silver cathode was studied at 300-450 °C and was compared with that of silver cathodes that were fabricated by the typical sputtering method. Inkjet-printed silver cathodes showed lower electrochemical impedance due to their porous structure, which facilitated oxygen gaseous diffusion and oxygen surface adsorption-dissociation reactions. A typical sputtered nanoporous silver cathode became essentially dense after the operation and showed high impedance due to a lack of oxygen supply. The results of long-term fuel cell operation show that the cell with an inkjet-printed cathode had a more stable current output for more than 45 h at 400 °C. A porous silver cathode is required for high fuel cell performance, and the simple inkjet printing technique offers an alternative method of fabrication for such a desirable porous structure with the required thermal-morphological stability.
